Process for the alkylation of compounds and the isomerization and conversion of alkyl-compounds



Patented May-3, '1938 :PATENT- OFFICE PROCESS FOR THE'ALKYLATION OF COM- POUNDS AND THE-ISOMERIZATION AND CONVERSION OF ALKYL-COMPOUND'S Karl; Schiillkopf, DuSseldorf-OberkasseL- Germany, assignor to the firm Rheinische Kampfer-Fabrik G. m. b. H., Dusseldorf-Oberkassel,

Germany No Drawing. Application August 22, 1929, Serial No. 387,819. In Germany September 17, 1928 6 Claims. (01. 260- 168) The' present invention relates to a process for the catalytic' 'alkylation of organic compounds and consists in attaching" olefinic hydrocarbons to the compounds-to be 'alkylated with the aid 5 .of certaincatalystsunder the influence of heat. Thisprocess of alkylation is to be understood to include thezintroductlon of alkyl, cycloalkyl and-aralkyl groups into the organic compounds. The use of catalysts or contact substances and conden'sation agents for the above-mentioned alkylating reaction is, it is true, already known. Thus,"metal saltsyparticularly aluminium chlorideymin'eral'acids," such as sulphuric acid, and metal oxides, such as aluminium oxide and thorioxide, ihave hitherto been used as catalysts of this kind.

It has nowlbeen'found that in place of the catalysts mentioned above, bleaching earths, ac-

tivated by treatment with acids, as well as clays, kaolins and similar silicates, activated in like manner mayv also be employed with particular advantage for eifecting alkylation. These surface catalysts in the main consist of hydro-silicates of aluminium, magnesium and iron and a free hydrated-silicic acidand are referred to in the following as activated hydro-silicates. By further treating these activated hydrosilicates with acids,'such as hydrochloric acid or sulphuric acid, the basic constituents, such as 30 aluminium oxide, magnesium oxide and iron oxide are almost completely dissolved out. The resulting hydrated silicic acids are also well adaptedas catalysts for efiecting alkylation. The use of activated hydro-silicates and hy- 35 drated silicic acids obtained therefrom by decomposition with acids as alkylation catalysts was hitherto not known. Besides their low cost these contactsubstances possess various other a advantages over the catalysts hitherto employed. 40 Thus, the catalytic activity of the above-mentioned new contact substances is considerably greater than that of aluminium oxide.

The attachment of the olefinic hydrocarbons,

- for example ethylene, propylene, cyclohexene,

45 'styrol'CsHs.CH -=CHz and the like, to cyclic hydrocarbon compounds, which include, besides the hydrocarbons proper, such as benzene or naph acids, that is, carboxyllc derivatives of cyclic hydrocarbons, with the formation of esters. For example by attachment of propylene to benzoic acid with the aid of said contact substances the isopropyl ester of benzoic acid is obtained. 5 It is also possible to effect alkylation at the nitrogen atom as well as alkylation at the carbon and oxygen atoms with the aid of the activated hydro-silicates and the hydrated silicic acids obtained therefrom. Thus, with the aid of these 10 contact substances olefinic hydrocarbons may be attached to aromatic amines with the formation of alkylated amines, that is, amino derivatives of cyclic hydrocarbons. For example by attaching olefinic hydrocarbons to aromatic amines, for ex- 15 ample aniline or naphthylamine, the corresponding products alkylated at the nitrogen atom may be obtained.

The following examples serve to show how the catalytic alkylation by attaching oleflnic hydrocarbons to the compounds to be alkylated may be effected by means of activated hydro-silicates and hydrated silicic acids obtained therefrom, it being understood, however, that the methods of application of these new contact substances are not limited to the described mode of action.

1. Naphthalene together with 20% of one of the commercial activated bleaching earths, for example Tonsi1", (a registered trade-mark) is treated with stirring in an autoclave at about 230 C. with ethylene under a pressure of about 20-40 atmospheres. After an equimolecular quantity of ethylene has become attached to the naphthalene in the course of several hours, the reaction product is separated from the catalyst by filtering or centrifuging and subjected to fractional distillation. The first runnings consist of unchanged naphthalene followed by the main fraction consisting of a liquid mixture of isomeric mono-ethyl naphthalenes having a boiling point of about 250-260 C., whilst the second runnings consist of high boiling poly-ethyl naphthalenes.

If the process is carried out for a longer time under the above-mentioned experimental conditions with twice the quantity or even more of ethylene, poly-ethyl naphthalenes are predominantly obtained. In place of ethylene, cracking gases containing ethylene and other olefines may also be employed and, in place of naphthalene, products having a high naphthalene content. The resulting alkylation products are highly valuable oils.

2. Benzoic acid is treated at about 230 C. in an autoclave with stirring together with 20% of "TonsiP with propylene under a pressure of 66 about -60 atmospheres. After an equimole'cular quantity of propylene'has been absorbed in,

the course of several hours, the reaction mixture is made alkaline and distilled with steam. A good yield of the isopropyl ester of benzoic aci of boiling point 218 C. is obtained.

3. 4 chloro-meta-cresol (6 chloro- 3 -oxy-lmethyl-benzene) is heated in an autoclave with 20% of Tonsil to 140 C.160 C. and propylene In place of the activated bleaching earthsemployed in Examples 1-3, kaolins, which have been partially decomposed by heating to 'C.-120 C. for several hours with 25% sulphuric acid, may also be employed. Further the bleaching earths or kaolins and similar silicates may be converted by a fairly long treatment with strong hydrochloric acid or sulphuric acid at about loo- C. into the corresponding hydrated silicic acids and the latter employed as contacts after washing out the mineral acids and drying on the water bath. 1

What I claim is:

1. In the alkylation of organic compounds, the process which comprises reacting together at elevated temperatures an oleflnic hydrocarbon and an aromatic hydrocarbon selected from the group consisting of benzene and naphthalene, in the presence oi! an activated hydro-silicate catalyst.

2. In the alkylation of organic compounds, the process which comprises reacting together at ele "vated an olefinic hydrocarbon and icsft'e saunas, J v 3. In the .alk ylationof'organic compounds, the process which comprises reacting together at elevated temperatures an oleflnic hydrocarbon and naphthalene in the presence of an activa-t hydro-silicate catalyst.

4. In the alkylation of organic compounds, the process whichcomprises reacting together at elevated temperatures an oleflnic hydrocarbon and no in of an activated anon-phenolic aromatic compound, free from phenolic-hydroxyl groups, in the presence of an activated hydro-silicate catalyst and distilling the reaction product to recover two fractions, one

containing mono-alkylated compounds and the other containing poly-alkylated compounds.

.5. In theallavlation of organic compounds, the process which comprises reacting together at elevated temperatures an oleflnic-hydrocarboa and a non-phenolic aromatic comppund, in the presence of. a surface catalyst, distilling the reaction product to recover two fractions, one containing m'ono-alkylated compounds and the other containlng poly-alkylated compounds, and reacting the fraction containing said poly-alkylated compounds with an additional cyclic hydrocarbon compound in the presence of said catalyst, thereby equilibrating the mixture.

6. In the, alkylation oi organic compounds, process which comprises reacting together at elevated temperatures an olefinic hydrocarbon and naphthalene in the presence of a surface KARL scnomxorr. 

